CN102627748A - Preparation method of acidic ionic liquid resorcinol formaldehyde resin copolymer material - Google Patents
Preparation method of acidic ionic liquid resorcinol formaldehyde resin copolymer material Download PDFInfo
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- CN102627748A CN102627748A CN2012100830319A CN201210083031A CN102627748A CN 102627748 A CN102627748 A CN 102627748A CN 2012100830319 A CN2012100830319 A CN 2012100830319A CN 201210083031 A CN201210083031 A CN 201210083031A CN 102627748 A CN102627748 A CN 102627748A
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Abstract
The invention discloses a preparation method of an acidic ionic liquid resorcinol formaldehyde resin copolymer material, and belongs to the technical field of organic chemical synthesis. The method is characterized by comprising the steps of: reacting vinyl pyridine compound with sultone to obtain ethylenic bond-containing sulfonic ylid; acidulating by sulfuric acid to obtain sulfonic functionalized ionic liquid monomer with anion of acid radical; carrying out self-assembly on the ionic liquid monomer to form an ionic liquid polymer solution; and then adding resorcinol and formaldehyde in the ionic liquid oligomer solution; condensing at 65-95 DEG C for 60-120 hours; carrying out rotary evaporation to dryness; and placing at 180-300 DEG C for condensation reaction for 2-32 hours to obtain the acidic ionic liquid resorcinol formaldehyde resin copolymer material. The material synthesized by the method of the invention has advantages of high thermal stability, high acid value and good catalytic effect.
Description
Technical field:
The present invention relates to the organic chemistry synthesis technical field, particularly a kind of preparation method of acidic ion liquid resorcinol formaldehyde resin copolymeric material.
Background technology:
Crisis occurs now in energy problem, environmental problem, do not produce unnecessary by product with a spot of energy and only generate the target that the purpose product becomes the modern chemical industry pursuit effectively.Acid catalyst is absolutely necessary in the chemical in modern times industry, is widely used in the manufacturing of variety of products such as medicine, petrochemical industry product, macromolecule product, but the most liquid acid catalyst as hydrochloric acid, sulfuric acid and so on that uses at present.The liquid catalyst that uses in process of production need be neutralized by alkali, through removing the operations such as salt that generated by neutralization, from product, separates, reclaims.But removing of above-mentioned neutralization and salt consumes quite a few energy in the operation.In addition, the salt excess supply that on market, reclaims, it is the little by product of operability mostly, therefore is difficult to usually handle.
With respect to above-mentioned situation; Because solid acid catalyst can not generate unnecessary by product in the operation of removing of separating, do not need when reclaiming above-mentioned neutralization or salt, and energy-conservation ground manufacturing purpose product; Therefore the research of this respect has received scientific worker's concern (Ishihara, K; Hasegawa, A; Yamamoto, H. Angew.Chem.Int.Ed.2001,40,4077.).Aspect the research and development of solid acid catalyst, solid acid catalysts such as zeolite, silica-alumina, moisture niobium have become the huge achievement of chemical industry, bring very big contribution to society.In addition,, can think that the material that the PS sulfonation is obtained is a solid acid, in the past always as having the tart Zeo-karb as the strong acid polymkeric substance.In addition, the known Nafion (registered trademark of E.I.Du Pont Company) that in the tetrafluoroethylene skeleton, has sulfo group also is the extremely strong solid acid (solid super-strong acid) of possess hydrophilic property, and the super acids that known their conducts have greater than the strength of acid of liquid acid works.But, the problem of selling at exorbitant prices when using is arranged in pair thermally labile, the industry.According to above-mentioned situation, consider that from aspects such as performance and costs use solid acid catalyst than using aforesaid liquid acid and more be difficult to design favourable industrial processes, nearly all now chemical industry all depends on liquid acid catalyst.Ionic liquid receives the attention of Chinese scholars always as a kind of environmental protection catalyzer and reaction solvent.But ionic liquid recovery in use particularly after reacting with bigger alcohols, the carboxylic-acid substance of polarity, can't be reclaimed owing to can be dissolved in delamination in the organism.
For addressing the above problem, the present invention considers to prepare a kind of acidic ion liquid resorcinol formaldehyde resin copolymeric material, on the basis that keeps the ionic liquid high catalytic activity, simplifies the removal process of material.In traditional pyridines ionic liquid, introduce polymerisable double bonds, through with resorcinol formaldehyde copolymerization, synthetic acidic ionic liquid resorcinol formaldehyde resin copolymeric material.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of acidic ion liquid resorcinol formaldehyde resin copolymeric material, the ionic liquid of this method preparation is recycled easy; Thermostability is high; Stable to water; The acid kind is many; Excellent catalytic effect.
The technical scheme that the present invention takes is following:
A kind of preparation method of acidic ion liquid resorcinol formaldehyde resin copolymeric material is characterized in that: with vinylpyridine compounds and sultone reaction, obtain containing the sulfonic inner salt of ethylene linkage; Carry out acidifying with sulfuric acid again; Obtaining negatively charged ion is the sulfonic functional ion liquid monomer of acid group, then the ionic liquid monomer is carried out autohemagglutination, forms ion liquid polymer solution; In ionic liquid oligomerization thing solution, add Resorcinol and formaldehyde again; Condensation is after 60～120 hours under 65～95 ℃ of conditions, revolves to steam to doing, placing to carry out condensation reaction under 180～300 ℃ and promptly got acidic ion liquid resorcinol formaldehyde resin copolymeric material in 2～32 hours.
Further be provided with and be:
Described vinylpyridine compounds is any one of 4-vinylpyridine, 2-vinylpyridine, 4-allyl pyridine.
The mol ratio of described Resorcinol and formaldehyde is 1:1～1:3, and the monomeric mol ratio of Resorcinol and acidic ion liquid is 1:0.1～1:2.
A kind of preparation method of acidic ion liquid resorcinol formaldehyde resin copolymeric material is characterized in that: with the vinylpyridine compounds is raw material, is after propane sultone or the butane sultone of 1:1 mixes with material molar ratio; After stirring 12～72 hours under the room temperature condition, obtain inner salt, with inner salt water-soluble after, with etc. the sulfuric acid of amount stir in room temperature; After forming homogeneous phase; Add the azo isobutyronitrile initiator, initiator amount is 0.5% of an ionic liquid monomer mass, forms ion liquid polymer solution after 12 hours carrying out the heated and stirred polymerization under 80 ℃; Adding is the Resorcinol of 1:0.1～1:2 with the ionic liquid monomer mole ratio again; With the Resorcinol mol ratio be the formaldehyde solution of 1:1～1:3, condensation after 60～120 hours under 65～95 ℃ of conditions is revolved and is steamed to doing; Place at last and carry out condensation reaction 2～32 hours under 180～300 ℃, promptly get acidic ion liquid resorcinol formaldehyde resin copolymeric material.
A kind of preparation method of acidic ion liquid resorcinol formaldehyde resin copolymeric material is characterized in that, may further comprise the steps:
The preparation of the 1st step, inner salt:
According to the ratio of amount is 1: 1 consumption, takes by weighing vinylpyridine compounds and sultone, at room temperature stirs after 12～72 hours and obtains solid salt; Suction filtration then; With mass concentration greater than 99% ether or ETHYLE ACETATE washing 3 times after, 60 ℃ are carried out vacuum drying, obtain inner salt;
The 2nd step, acidifying:
Inner salt is dissolved in the ethanol, adds sulfuric acid, the vitriolic consumption equates with the amount of inner salt; At room temperature mixed 4 hours, and obtained the ionic liquid solution that corresponding negatively charged ion is a bisulfate ion, under 50 ℃, carry out underpressure distillation; Remove etoh solvent, obtain the ionic liquid monomer;
Synthesizing of the 3rd step, ion liquid polymer:
The ionic liquid monomer is dissolved in the water; The consumption of water is 5～10 times of ionic liquid monomer mass; Add the azo isobutyronitrile initiator again, initiator amount is 0.5% of an ionic liquid monomer mass, forms ion liquid polymer solution after 12 hours carrying out the heated and stirred polymerization under 85 ℃;
The 4th step, acidic ion liquid resorcinol formaldehyde resin copolymeric material synthesize:
Adding is the Resorcinol of 1:0.1～1:2 with the ionic liquid monomer mole ratio in above-mentioned ion liquid polymer solution; With the Resorcinol mol ratio be the formaldehyde solution of 1:1～1:3; Condensation is after 60～120 hours under 65～95 ℃ of conditions; Revolve and steam, place at last and carry out condensation reaction 2～32 hours under 180～300 ℃, promptly get acidic ion liquid resorcinol formaldehyde resin copolymeric material to doing.
The present invention compared with prior art has following beneficial effect:
(1) thermally-stabilised qualitative height, heat decomposition temperature is more than 208 ℃.
(2) acid number is high, more than 4.0mmol/g.
(3) recovery is easy, can separate through simple filtration.
(4) excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. have very high catalytic activity.
(5) catalyzer can repeat repeatedly to use.
Below will do further elaboration to the present invention through concrete embodiment:
Embodiment:
One, preparation embodiment.
The preparation of embodiment 1,4-ethene imidazoles sulfate ion liquid resorcinol formaldehyde resin copolymeric material.
The preparation of the 1st step, inner salt:
According to the ratio of amount is 1: 1 consumption, takes by weighing the 4-vinylpyridine and third sultone, at room temperature stirs after 72 hours and obtains solid salt; Suction filtration then; With mass concentration greater than 99% ether or ETHYLE ACETATE washing 3 times after, 60 ℃ are carried out vacuum drying, obtain inner salt;
The 2nd step, acidifying:
Inner salt is dissolved in (1 gram solid is to 5 gram ethanol) in the ethanol; Add sulfuric acid, the vitriolic consumption equates with the amount of substance of inner salt, at room temperature mixes 4 hours; Obtain the ionic liquid solution that corresponding negatively charged ion is a bisulfate ion; Under 50 ℃, carry out underpressure distillation, remove etoh solvent, obtain the ionic liquid monomer;
Synthesizing of the 3rd step, ion liquid polymer:
The ionic liquid monomer is dissolved in the water; The consumption of water is 10 times of ionic liquid monomer mass; Add the azo isobutyronitrile initiator again, initiator amount is 0.5% of an ionic liquid monomer mass, forms ion liquid polymer solution after 12 hours carrying out the heated and stirred polymerization under 85 ℃;
The 4th step, acidic ion liquid resorcinol formaldehyde resin copolymeric material synthesize:
Adding is the Resorcinol of 1:1 with the ionic liquid monomer mole ratio in above-mentioned ion liquid polymer solution; With the Resorcinol mol ratio be the formaldehyde solution of 1:1.3, condensation after 60 hours under 70 ℃ of conditions is revolved and is steamed to doing; Place at last and carry out condensation reaction 4 hours under 180 ℃; Promptly get acidic ion liquid resorcinol formaldehyde resin copolymeric material, the material acid number is 4.6mmol/g, 220 ℃ of thermotolerances.
Embodiment 2-4:
The preparation method is with embodiment 1, and difference is to adopt different pyridine compounds and theirs, and the acidic ion liquid resorcinol formaldehyde resin copolymeric material performance of its preparation is as shown in table 1.
Table 1: the acidic ion liquid resorcinol formaldehyde resin copolymeric material performance table of different pyridine compounds and their preparations.
| Embodiment | Pyridine | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 2 | The 3-vinylpyridine | 4.5 | 218 |
| 3 | The 2-vinylpyridine | 4.4 | 216 |
| 4 | The 4-allyl pyridine | 4.3 | 210 |
。
Embodiment 5-7
The preparation method is with embodiment 1, and it is as shown in table 2 with the acidic ion liquid resorcinol formaldehyde resin copolymeric material performance that the ionic liquid monomer ratio prepares that difference is to adjust Resorcinol.
Table 2: the acidic ion liquid resorcinol formaldehyde resin copolymeric material performance table of different Resorcinols and the preparation of ionic liquid monomer ratio.
| Embodiment | N (ionic liquid monomer)/n (Resorcinol) | Acid number/mmol/g | Heat decomposition temperature/℃ |
| 5 | 1：0.5 | 5.6 | 208 |
| 6 | 1：1.2 | 4.3 | 221 |
| 7 | 1:1.5 | 4.0 | 225 |
。
Two, application implementation example.
Acidic ion liquid resorcinol formaldehyde resin copolymeric material with embodiment 1 preparation is used for catalytic esterification, condensation reaction, alkylated reaction, etherification reaction, gets following embodiment.
Embodiment 8, catalytic esterification:
Having induction stirring, TM, reflux condensing tube; Adding 0.1mol Hydrocerol A, 0.45mol propyl carbinol carry out heated and stirred in the 100mL three-necked bottle of water trap, treat that Hydrocerol A dissolves back sampling and measuring acidity entirely, adds the catalyzer of 0.25g then; Carrying out reflux stirs; The water that reaction is produced is told from water trap, reaction 4h, and calculated yield is 99.1%.
Embodiment 9-13:
Except that following difference, all the other are with embodiment 8: after reaction finished, catalyzer carried out filtered and recycled, behind washing with acetone, place 100 ℃ of baking oven dryings after, continue reaction, the result sees table 3.
Table 3: catalyzer reuse number of times is to the influence of catalytic performance.
| Embodiment | Catalyzer reuse number of times | Productive rate/% |
| 9 | 0 | 99.1 |
| 10 | 1 | 99.0 |
| 11 | 2 | 98.6 |
| 12 | 3 | 98.0 |
| 13 | 4 | 97.9 |
。
Embodiment 14, catalyzing and condensing reaction:
Having induction stirring; Reflux condensing tube; Add 0.1mol pimelinketone, 0.15mol terepthaloyl moietie, 10ml hexanaphthene and 0.1g catalyzer in the 100mL three-necked bottle of water trap, carry out the reflux stirring water and the entrainer azeotropic of reaction generation are steamed, about reaction 1.5h; Yield is reused 5 times for the 99.5%. catalyzer, and catalytic activity does not change.
Embodiment 15, catalytic alkylation reaction:
Having induction stirring, reflux condensing tube adds 0.1mol pyrocatechol, the 0.15mol trimethyl carbinol and 0.1g catalyzer in the 100mL three-necked bottle of water trap; Carrying out reflux stirs; About reaction 4h, yield is that 83%. catalyzer are reused 5 times, and catalytic activity does not change.
Embodiment 16, catalyst etherifying reaction:
Having induction stirring, reflux condensing tube adds 0.1mol2-naphthols, 0.15mol methyl alcohol and 0.1g catalyzer in the 100mL three-necked bottle of water trap, carry out reflux and stir, and about reaction 6h, yield is that 88%. catalyzer are reused 5 times, and catalytic activity does not change.
Claims (5)
1. the preparation method of an acidic ion liquid resorcinol formaldehyde resin copolymeric material is characterized in that: with vinylpyridine compounds and sultone reaction, obtain containing the sulfonic inner salt of ethylene linkage; Carry out acidifying with sulfuric acid again; Obtaining negatively charged ion is the sulfonic functional ion liquid monomer of acid group, then the ionic liquid monomer is carried out autohemagglutination, forms ion liquid polymer solution; In ionic liquid oligomerization thing solution, add Resorcinol and formaldehyde again; Condensation is after 60～120 hours under 65～95 ℃ of conditions, revolves to steam to doing, placing to carry out condensation reaction under 180～300 ℃ and promptly got acidic ion liquid resorcinol formaldehyde resin copolymeric material in 2～32 hours.
2. the preparation method of a kind of acidic ion liquid resorcinol formaldehyde resin copolymeric material according to claim 1 is characterized in that: described vinylpyridine compounds is any one of 4-vinylpyridine, 2-vinylpyridine, 4-allyl pyridine.
3. the preparation method of a kind of acidic ion liquid resorcinol formaldehyde resin copolymeric material according to claim 1; It is characterized in that: the mol ratio of described Resorcinol and formaldehyde is 1:1～1:3, and the monomeric mol ratio of Resorcinol and acidic ion liquid is 1:0.1～1:2.
4. the preparation method of a kind of acidic ion liquid resorcinol formaldehyde resin copolymeric material according to claim 1 is characterized in that: with the vinylpyridine compounds is raw material, is after propane sultone or the butane sultone of 1:1 mixes with material molar ratio; After stirring 12～72 hours under the room temperature condition, obtain inner salt, with inner salt water-soluble after, with etc. the sulfuric acid of amount stir in room temperature; After forming homogeneous phase; Add the azo isobutyronitrile initiator, initiator amount is 0.5% of an ionic liquid monomer mass, forms ion liquid polymer solution after 12 hours carrying out the heated and stirred polymerization under 80 ℃; Adding is the Resorcinol of 1:0.1～1:2 with the ionic liquid monomer mole ratio again; With the Resorcinol mol ratio be the formaldehyde solution of 1:1～1:3, condensation after 60～120 hours under 65～95 ℃ of conditions is revolved and is steamed to doing; Place at last and carry out condensation reaction 2～32 hours under 180～300 ℃, promptly get acidic ion liquid resorcinol formaldehyde resin copolymeric material.
5. the preparation method of a kind of acidic ion liquid resorcinol formaldehyde resin copolymeric material according to claim 1 is characterized in that, may further comprise the steps:
The preparation of the 1st step, inner salt:
According to the ratio of amount is 1: 1 consumption, takes by weighing vinylpyridine compounds and sultone, at room temperature stirs after 12～72 hours and obtains solid salt; Suction filtration then; With mass concentration greater than 99% ether or ETHYLE ACETATE washing 3 times after, 60 ℃ are carried out vacuum drying, obtain inner salt;
The 2nd step, acidifying:
Inner salt is dissolved in the ethanol, adds sulfuric acid, the vitriolic consumption equates with the amount of inner salt; At room temperature mixed 4 hours, and obtained the ionic liquid solution that corresponding negatively charged ion is a bisulfate ion, under 50 ℃, carry out underpressure distillation; Remove etoh solvent, obtain the ionic liquid monomer;
Synthesizing of the 3rd step, ion liquid polymer:
The ionic liquid monomer is dissolved in the water; The consumption of water is 5～10 times of ionic liquid monomer mass; Add the azo isobutyronitrile initiator again, initiator amount is 0.5% of an ionic liquid monomer mass, forms ion liquid polymer solution after 12 hours carrying out the heated and stirred polymerization under 85 ℃;
The 4th step, acidic ion liquid resorcinol formaldehyde resin copolymeric material synthesize:
Adding is the Resorcinol of 1:0.1～1:2 with the ionic liquid monomer mole ratio in above-mentioned ion liquid polymer solution; With the Resorcinol mol ratio be the formaldehyde solution of 1:1～1:3; Condensation is after 60～120 hours under 65～95 ℃ of conditions; Revolve and steam, place at last and carry out condensation reaction 2～32 hours under 180～300 ℃, promptly get acidic ion liquid resorcinol formaldehyde resin copolymeric material to doing.
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Cited By (6)
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| CN104151164A (en) * | 2014-07-17 | 2014-11-19 | 中国科学院过程工程研究所 | Method for preparing methyl chloroacetate |
| CN104492482A (en) * | 2014-11-26 | 2015-04-08 | 绍兴文理学院 | Polymerized ionic liquid-silicon dioxide composite solid acid and preparation method thereof |
| CN105772083A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Resin-supported anionic acidic ionic liquid catalyst and application thereof |
| CN109575207A (en) * | 2018-11-29 | 2019-04-05 | 常州大学 | A method of using imidazoles double-core basic functionalized ionic liquid as catalyst preparation phenolic resin microspheres |
| CN110354897A (en) * | 2019-02-19 | 2019-10-22 | 河北科技大学 | A kind of preparation method and application of acidity polymeric ionic liquid resin catalyst |
| CN111533837A (en) * | 2020-04-20 | 2020-08-14 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151164A (en) * | 2014-07-17 | 2014-11-19 | 中国科学院过程工程研究所 | Method for preparing methyl chloroacetate |
| CN104492482A (en) * | 2014-11-26 | 2015-04-08 | 绍兴文理学院 | Polymerized ionic liquid-silicon dioxide composite solid acid and preparation method thereof |
| CN105772083A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院兰州化学物理研究所 | Resin-supported anionic acidic ionic liquid catalyst and application thereof |
| CN105772083B (en) * | 2014-12-16 | 2018-09-25 | 中国科学院兰州化学物理研究所 | A kind of resin-carried anionic acid ionic-liquid catalyst and its application |
| CN109575207A (en) * | 2018-11-29 | 2019-04-05 | 常州大学 | A method of using imidazoles double-core basic functionalized ionic liquid as catalyst preparation phenolic resin microspheres |
| CN110354897A (en) * | 2019-02-19 | 2019-10-22 | 河北科技大学 | A kind of preparation method and application of acidity polymeric ionic liquid resin catalyst |
| CN110354897B (en) * | 2019-02-19 | 2022-04-26 | 河北科技大学 | Preparation method and application of acidic polymerization ionic liquid resin catalyst |
| CN111533837A (en) * | 2020-04-20 | 2020-08-14 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
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